【作者】 高建纲；

【导师】 张其锦；

【作者基本信息】 中国科学技术大学 ， 高分子化学与物理， 2007， 博士

【摘要】 以环糊精为主体分子通过分子识别进行自组装的研究是目前超分子化学研究的一个重要领域。本文通过制备β-环糊精与系列长链二元酸的包合物，探讨和分析了β-环糊精与二元酸体系超分子自组装形成包合物的过程以及包合物的结构；在此基础上制备β-环糊精与二元酸二负离子包合物并研究了包合体系在水溶液中的构象；利用长链脂肪族二元酸的疏水链段结构，通过缩聚的方法制备了系列两亲性缩聚物并进一步研究了缩聚物与β-环糊精的包合行为；对于形成包合物的体系进行了包合机理分析。具体内容如下：1．利用共沉淀法和圆相研磨法两种不同的方法制得了β-环糊精与系列长链二元酸的超分子自组装制备包合物；运用傅立叶变换红外光谱、差热分析、元素分析、X-射线衍射分析确证了包合物的形成；包合物中β-环糊精与二元酸的物质的量比为2：1；β-环糊精分子通过氢键及疏水相互作用包覆于二元酸分子表面，形成了管道状的[3]准轮烷结构。2．在化学计量比为2：1的β-环糊精与二元酸包合物的基础上，通过包合物与碱作用，得到β-CD与二元酸双负离子的包合物；通过红外光谱、核磁共振氢谱证实该包合物经过NaOH处理形成β-环糊精与二元酸双负离子包合物的过程中保持了两个β-环糊精分子与二元酸亚甲基链包合形成的[3]准轮烷结构。3．以游离态的β-环糊精作为基准，在比较1：1包合的β-环糊精与二元酸双负离子和2：1的β-环糊精与二元酸双负离子包合物核磁共振谱图对应氢原子核磁共振峰的基础上，结合目前已知的相关理论，确定了化学计量比为1：1的β-环糊精与二元酸双负离子包合物中亚甲基骨架采取了gauche纽结后的排列方式，β-环糊精分子与8个亚甲基相包合；而2：1的β-环糊精与二元酸双负离子包合物中亚甲基链采取了反式构象，每个β-环糊精分子与4个亚甲基进行包合。通过二维核磁谱进一步确定了其包合模式为[3]准轮烷结构。4．通过缩聚反应制备了二元酸之一(DA13)与未封端及单甲氧基封端PEG-的四种两亲性缩聚物；在环糊精饱和水溶液体系中，利用共沉淀法，通过加入缩聚物客体分子，成功地制得并离心分离出了CP613、CP1113、CP2013与β-环糊精的包合物。5．通过红外光谱、X-射线衍射及核磁共振谱分析确认了三种缩聚物包合物的形成；通过~1H-NMR分析了包和物中β-环糊精与缩聚物分子链的包合情况，由相关氢的核磁共振峰的峰形确定了包合物中主客体分子间的包合位点，通过积分面积比计算出包合物中β-环糊精分子链数目的包合比例。6．针对碳原子数为13的二元酸与单羟基封端的缩聚物(CP1113)具有的明确的三嵌段结构，运用紫外一可见吸收光谱法、差示扫描量热及核磁共振谱等方法分析了CP1113与β-环糊精的包合过程；确定了CP1113上PEO链节与β-CD分子的数目比为7.5：1；因此β-环糊精除部分相对固定在酯羰基附近和在疏水结构中心亚甲基链节上滑动外，其余大部分环糊精分子与PEO链段进行了包合；7．CP1102由于中心疏水链段过短，不能有效地形成缩聚物链与环糊精相互作用的稳定中心，因此与β-CD作用没有包合物形成；CP5013则可能由于两端的PEG链较长，与环糊精包合需要克服更高的能垒，因此也未能形成包合物。根据以上分析结果，提出了β-环糊精与三嵌段缩聚物CP1113的包合模型；该模型通过改变缩聚物的结构及对应的环糊精与缩聚物分子链的数目比例，可以用来解释其他缩聚物与β-环糊精包合物的形成过程。更多还原

【Abstract】 In supramolecular chemistry, it is important to study the self-assemblingbehaviors through molecular-recognition with cyclodextrins as the host molecules.In this paper, based on the preparation of inclusion complexes （ICs） betweenβ-cyclodextrin（β-CD） and a series of long-chain aliphatic diacids（DAn,n varing from11 to 15）, the supramolecular assembling behaviors of the above systems werestudied and the corresponding ICs were characterized to determine theirpseudorotaxane structures. The ICs ofβ-CD and a,?-alkanedicarboxylate anions(DAn^2-) were acquired and the structure together with the conformation in aqueoussolution was characterized and proved to be also a pseudorotaxane structure. A seriesof amphiphilic condensation polymers（polyesters） were synthesized utilizing thephobic chains of DAn by condensation polymerization with PEG andmono-hydoxyl-PEG, then the inclusion behaviors between these polymers andβ-CDwere studied and the process,the michanism of ICs-forming systems wereinvestigated. All the details are as follows:1.The inclusion complexes ofβ-CD and DAn were prepared by co-precipitationand co-grinding via supramolecular assembling and the formation of ICs wereconfirmed by means of FTIR、DTA、elementary analysis and XRD analysis; thestoichiometry ofβ-CD to DAn was 2:1 and theβ-CD molecules were accomodatedon the aliphatic chain of DAn to form a columar [3]pseudorotaxane structure.2. On the basis of the ICs ofβ-CD and DAn,β-CD and a,?-alkanedicarboxylateanions (DAn^2-) were acquired by neutrilization with base and the [3]pseudorotaxanestructure was maintained by FFIR and H-NMR analysis.3. By comparing the H-NMR spectra of the IC ofβ-CD and a,?-alkanedi-carboxylate anions with 1:1 molar ratio with that of 2:1, it is reached that in the 1:1IC, the methylene chain of DAn^2- adopts a gauche kink conformation and themaximum number of carbon atoms in the aliphatic hydrocarbon chain is 8. Otherwise,the methylene chain of DAn^2- in 2:1 IC adopts a trans-conformation to make 4 carbonatoms in the aliphatic hydrocarbon chain resided in oneβ-CD molecules. 2D-NOSEY spectrum ulteriorly confirmed that the including mode was a [3]pseudorotaxanestructure.4.A series of amphiphilic condensation polymers（polyesters） were synthesizedutilizing the phobic chains of DAn by condensation polymerization with PEG andmono-hydoxyl-PEG. The inclusion behaviors between these polymers andβ-CD werestudied and ICs of CP613、CP1113、CP2013 were acquired by co-precipitation fromβ-CD saturated aqueous solution and seperated by centrifugation.5.The formation of ICs above was confirmed by FTIR、XRD and H-NMRspectra and the accomodating situations were determined by the shape of NMRresonance peaks and the stoichiometry of the complexes is ofβ-CD to DAn wasachieved by calculation of area integral.6.Especially for CP1113 synthsized by DA13 condensating withmono-hydroxyl-PEG, which has a specific tri-block structure, the process of theIC-forming was studied by UV-vis spectrum、DSC、TG and H-NMR analysis and thethe stoichiometry ofβ-CD to PEO segments was 7.5:1, so part ofβ-CD moleculeswere accomodated on the hydrofobic methylene chain and most ofβ-CD moleculeswrapped on PEO segments of CP1113.7. No inclusion complex of CP1102 was formed possibly due to the shorterhydrofobic hydrocarbon chain and the weaker interactions withβ-CD led to thedifficulty for supramolecular assembling. For CP5013, which was synthesized byDA13 and PEGS000, no inclusion complex was observed beacause the longer PEOchain and the higher energy level blocked theβ-CD molecules to thread. A inclusioncomplex-forming model was put forward according to the above experimental resultsand the model could explain the forming mechanism of all these ICs formed bycondensation polymers withβ-CD supposing the model was appropriately adjusted.更多还原